CN102216372B - Silicone-thermoplastic polymer reactive blends and copolymer products - Google Patents
Silicone-thermoplastic polymer reactive blends and copolymer products Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
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- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
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Abstract
Silicone-thermoplastic polymer reactive blends and copolymer products are prepared using economical post-reactor reactive mixing, e.g., extrusion. The procedure is based on the ring-opening polymerization of cyclic siloxanes within a thermoplastic polymer matrix. In a preferred mode, the thermoplastic polymer is a polyolefin, optionally containing silane groups that are available for reaction with the silicone polymer that is formed in situ. The resulting materials provide hybrid performance that can extend the range of applications beyond those which are served by thermoplastic polymers or silicones alone, or their physical blends.
Description
The cross reference of related application
The application requires the right of priority of the U.S. Patent application 61/085,638 of submission on August 1st, 2008, and its full content is incorporated the application into by reference.
Invention field
The present invention relates to organosilicon-thermoplastic polymer reactively blending thing and copolymerization product.On the one hand, the present invention relates to prepare the method for such blend and product, wherein make cyclic organic polymerization in polymer thermoplastic matrix, and on the other hand, the present invention relates to such method, wherein said thermoplastic polymer is randomly with the functionalized polyolefine of silane group, and described cyclic organic is in the auxiliary lower polymerization of ring opening catalyst.
Background of invention
Organosilicon polymer is used for various application, wherein organosilicon polymer is owing to the unique combination of their character has much value, and these character comprise thermostability, ozone resistance and weathering resistance, oxidative stability, oilness, water-repellancy, low surface tension, good electrical properties, cryogenic properties, oil resistant, moisture and steam, chemical resistant properties and flame retardant resistance.Reactively blending thing and the multipolymer of organosilicon and various thermoplastic polymer (particularly polyolefin polymer) can provide composite behaviour, this composite behaviour can the expanded application scope, and those ranges of application that provided by independent thermoplastic polymer or organosilicon polymer or their physical blending thing are provided for it.In addition, with respect to pure organosilicon polymer or pure thermoplastic polymer, these blends and multipolymer provide performance and/or cost advantage.
USP 5,488, and 087 has described the polyethylene of sulfonation and the blend of octamethylcyclotetrasiloxane, wherein the ring-opening polymerization of the sulfonic acid group catalyze siloxane on the polyethylene.Speed of reaction is quite slow, needs several weeks reaching the range of polymerization, and the both not also not instructions or advise that the organosilicon that obtains is to graft on polymkeric substance of the reaction mechanism of the organosilicon that obtains of instruction or suggestion and polymkeric substance of this reference.
U.S. Patent Application Publication 2006/0217460 has been described composition, and it comprises various polyolefine, inorganic combustion inhibitor and can be the organosilicon of ring-type.The surface of cyclic organic with applying fire retardant is provided.Said composition does not comprise the polyolefine that comprises grafted silane, and its undeclared cyclic organic can graft on polyolefine when polymerization forms siloxane polymer.In addition, the method for preparing siloxane polymer does not comprise catalyzer.Further again, the organic silicon coating of fire retardant formed before fire retardant is joined polyolefine.
U.S. Patent Application Publication 2006/0223943 has been described polyolefin graft copolymer, and the graft copolymerization by olefinic monomer and silicone macromolecule monomer (making by letex polymerization) in the situation that its transition metal complex coordination polymerization catalysts after ordination number leans on exists prepares.The silicone macromolecule monomer by organo-siloxane with in its molecule, comprise the reaction that has a compound of reactive functional group with organo-siloxane and make.
USP 5,854, and 356 have described the polyolefine of the organosilicon inarch for preparing by being mixed of organosilicon and reactive polyolefine (comprising vinyl-vinyl Trimethoxy silane multipolymer or ethylene-methyl methacrylate hydroxyethyl ester copolymer).The polyolefine of the organosilicon inarch that obtains has showed the superior demoulding (low adhesion) character, and described character can further be improved when using dibutyl tin laurate as condensation catalyst.The polyethylene that organosilicon is functionalized and the blend of unmodified polyethylene have also showed release property.
USP 6,054, and 548 have described the phosphazene base catalyzer that is used for the ring-opening polymerization of cyclic organic.Such catalyzer is not described for the organosilyl purposes in the polyolefin substrate.
The expectation Innovative method is mixed behind the economic reactor and/or extrusion equipment prepares organosilicon-thermoplastic polymer reactively blending thing and polymerisate in order to utilize.The present invention is limited for the preparation of the method for such reactively blending thing, and it comprises the interior chemistry of reactor or its reactive being mixed of the incompatible mixture of thermoplastic polymer and reluctant high molecular organosilicon polymer.
Summary of the invention
Organosilicon-thermoplastic polymer reactively blending thing and copolymerization product utilize economic reactor afterreaction mixing (for example, extruding) preparation.This process is based on the ring-opening polymerization of annular siloxane in polymer thermoplastic matrix.In preferred mode, thermoplastic polymer is the polyolefine that randomly comprises silane group, and described silane group can be used for the reaction of the organosilicon polymer that forms with original position.The material that obtains provides composite behaviour, and it can the expanded application scope, and those ranges of application that provided by independent thermoplastic polymer or organosilicon polymer or their physical blending thing are provided this range of application.In addition, with respect to pure thermoplastic polymer or organosilicon polymer, they provide performance and/or cost advantage.In one embodiment, the method uses phosphazene base as catalyzer.In another embodiment, the method comprises the reaction in－situ of monohydroxy organosilicon and silane-functionalised polymkeric substance.
In one embodiment, the present invention is the method for preparation feedback blend, wherein said blend comprises the organosilicon polymer in the polymer thermoplastic matrix, said method comprising the steps of: (A) form the mixture of annular siloxane and thermoplastic polymer, and (B) make described mixture stand to make the annular siloxane polymerization to be formed with the condition of organosilicon polymer.Preferably, use catalyzer to make the annular siloxane polymerization so that ring is opened.
In one embodiment, the present invention prepares to comprise to derive from thermoplastic polymer (being preferably polyolefin polymer), the independent methodology of the copolymerization product of the unit of silane crosslinker and organosilicon polymer, said method comprising the steps of: described silane crosslinker is contacted under the grafting condition with described thermoplastic polymer, so that described silane crosslinker grafts on described thermoplastic polymer, (ii) under the annular siloxane polymerizing condition, annular siloxane is joined in the thermoplastic polymer of described Silane Grafted so that described organosilicon polymer forms and with the thermoplastic polymer reaction of described Silane Grafted.In a kind of variant of present embodiment, first step and second step carry out in long forcing machine, and wherein first step carries out in the grafting zone carrying out in the ring-opening polymerization zone with second step.In the another kind of variant of present embodiment, grafting and open loop/polymerization procedure are simultaneously or approach and carry out simultaneously.
In one embodiment, the present invention is reactively blending thing or the multipolymer that includes the reaction product of organosilicon polymer and thermoplastic polymer (being preferably polyolefin polymer), and in another embodiment, the present invention is the polyolefinic reaction product of organosilicon polymer and Silane Grafted.Again in another embodiment, the present invention is by a kind of reactive blending thing or the copolymerization product for preparing in the aforesaid method.Again in another embodiment, the present invention is the goods that comprise reactively blending thing or copolymerization product.
Description of drawings
Fig. 1 is Fourier transform infrared (FTIR) figure that shows the formation of the open loop of octamethylcyclotetrasiloxane and polydimethylsiloxane.
Fig. 2 is the FTIR figure that shows open loop and the formation of polydimethylsiloxane in the situation that phosphazene base exists and in polyolefin substrate of octamethylcyclotetrasiloxane.
Embodiment
The all elements periodictable that the application mentions refers to the Press by CRC, and Inc. is in 2003 periodic table of elements of publishing and enjoy copyright.Equally, any family of mentioning should be the family of reflecting in this periodic table of elements of the IUPAC system that uses numbering family.Unless point out, from context hint or prior art convention, all parts and per-cent are all based on weight, and all testing method are synchronous with the application's submission date.Purpose for patent practice, the content of any patent, patent application or the application's reference all is incorporated herein by reference (or its US embodiment of equal value also is incorporated herein by reference) at this, particularly about the disclosure of the synthetic technology in this area, definition (any definition that does not specifically provide with the application is inconsistent) and general knowledge.
Digital scope among the application is approximation, unless therefore refer else, it can comprise this scope value in addition.Numerical range comprises all numerical value from the lower value to the higher limit that increase with 1 unit, and condition is in arbitrarily lower value and the arbitrarily interval of at least 2 units of existence between the high value.For example, if record component, physics or other character are 100 to 500 such as melt index or temperature, mean and enumerated clearly all single numerical value, such as 100,101,102 etc., and all subranges, such as 100 to 144,155 to 170,197 to 200 etc.For comprising less than 1 numerical value or comprising mark greater than 1 scope of (such as 1.1,1.5 etc.), regard 1 unit as 0.0001,0.001,0.01 or 0.1 in the time of suitably.For the scope of the units that comprises less than 10 (for example 1 to 5), typically regard 1 unit as 0.1.These only are the examples of the concrete content that means, and might making up of cited Schwellenwert and the numerical value between the maximum all is considered to clear record in this application.Digital scope in the application provides the grafting content of annular siloxane, thermoplastic polymer and/or catalyst content, thermoplastic polymer of density, melt index, reaction mixture and product and various processing parameters etc.
Term " comprises " and derivative is not intended to get rid of the existence of any other component, step or process, and no matter whether the application disclosed them especially.For eliminating any query, unless opposite explanation is arranged, otherwise, by use term " comprise " all compositions that require can comprise any other additive, auxiliary material or compound (no matter be polymerization or be not polymerization).On the contrary, except for unnecessary those of processing property, term " basically by ... form " will any other component, step or process get rid of outside the how lower scope of narrating in office.Term " by ... form " do not comprise any component, step or process of not describing especially or listing.Unless illustrate, "or" refer to listed separate member with and any combination.
When using about chemical compound, unless offer some clarification on, odd number comprises all isomeric form, and vice versa (for example, " hexane " comprises separately or jointly whole isomer of hexane).Term " compound " and " complex compound " are used for representing organic compound, mineral compound and organometallics interchangeably.No matter the minimum of term " atom " expression element forms, and ionic condition, that is, no matter whether it is charged or part is charged or be bonded in another atom.Term " amorphous " expression lacks such as the polymkeric substance by dsc (DSC) or the determined crystalline melting point of equivalent technique.
Terms such as " compositions " represents the mixture of two or more materials.Before comprising reaction in the composition, the mixture of reaction after the neutralization reaction, wherein will comprise unreacted components and the degradation production of the reaction mixture that components of mixture before reaction product and by product and (if existence) are by one or more reactions or reaction mixture form than the latter.
The term such as " blend " or " blend polymer " represents the mixture of two or more polymkeric substance.Such blend can be or can not be molten mixed.Such blend can or can not be separated.Such blend can comprise or can not comprise one or more microcell structures, as determined by transmitted electron spectral method, scattering of light, x-ray scattering and any other methods known in the art.
The terms such as " reactively blending thing ", " reactor in blend " represent the reaction product that the reaction mixture by two or more components makes, wherein said two or more components are reacted in the situation that one or more other components exist at least, or whole components is reacted substantially at the same time.Each component can with their id reactions (as in the situation of homopolymerization) or with other component in one or more the reaction (as in the situation of copolymerization or grafting).In the context of the present invention, an example of reactively blending thing is the reaction product that comprises polyolefine and organosilicon polymer, wherein organosilicon polymer forms in the situation that polyolefin polymer exists, that is, polyolefin polymer is the component that is formed with the reaction mixture of organosilicon polymer.Another example of reactively blending thing in the context of the invention is the reaction product that comprises Silane Grafted polyolefin polymer and organosilicon polymer, and wherein the Silane Grafted polyolefin polymer all makes at the same time and/or all made by identical reaction mixture with organosilicon polymer.
" physical blending thing ", terms such as " physical polymeric blends " represents reactor post polymerization thing blend, that is, and the result's who mutually mixes under the polymkeric substance condition that can not react to each other therein for two or more polymkeric substance blend.In the physical blending thing, each polymeric constituent is physical mixed each other, forms new larger molecule but not react to each other.
Terms such as " copolymerization products " represents the product that formed by two or more monomers or polymkeric substance reaction each other.In the context of the present invention, the example of copolymerization product is the product that the reaction by organosilicon polymer and silane-functionalised polyolefin polymer forms.
The term such as " reaction mixture ", " reactive material " represent typically under reactive conditions for reaction the combination of each material that must or reaction be helped out.Through whole reaction process, reaction mixture is converted into product mixtures.Whether intermittently depend on instantaneous moment (wherein characterizing reaction mixture) and other factors (physical condition of, initial substance or continuous such as method and product material etc.), it will comprise maybe can comprise reactant, catalyzer, solvent, processing aid, product, by product, impurity etc.
Terms such as " product mixtures " represents by making reaction mixture stand the combination of resulting each material of reaction conditions.Product mixtures will always comprise some products and/or by product, and (for example depend on the diversity of factor, intermittently with respect to the physical condition of continuous, initial substance etc.), it can comprise or can not comprise unreacted initial substance, catalyzer, solvent, processing aid, impurity etc.
The ordinary representation such as " reaction conditions " term is transformed to reaction mixture temperature, pressure, reactant concn, catalyst concn, cocatalyst concentration, mixing or the shearing etc. of reaction mixture.Reaction conditions not only affects speed of reaction and transformation efficiency and the selectivity that initial reactant forms reaction product, also often affects the character of reaction product.
Terms such as " open loop condition " represents that the ring of annular siloxane opens necessary reaction conditions in polymer thermoplastic matrix.These conditions will along with the existence of the character of polymeric matrix, siloxanes and structure, ring opening catalyst whether, whether the existence of processing additives waits and change.
Terms such as " polymerizing conditions " represents to make monomer in conjunction with forming the necessary reaction conditions of polymkeric substance.In the context of the present invention, these conditions are to make the annular siloxane of open loop interosculate to be formed with necessary those conditions of organosilicon polymer in polymeric matrix.
The macromolecular compound of " polymkeric substance " expression by monomer polymerization is prepared, and no matter whether described monomer is identical or different type.Therefore general term polymer comprises term homopolymer (only being commonly used to refer to the polymkeric substance by one type monomer preparation) and by with undefined term multipolymer.It also comprises the form of ownership of interpretation, for example, and random, block etc.Term " ethylene/alpha-olefin polymer ", " propylene/alpha-olefins polymkeric substance " and " silane copolymer " can represent interpretation described below.
" interpretation " expression expression is by the polymkeric substance of the polymerization preparation of at least two kinds of dissimilar monomers.This generality term comprises multipolymer (being commonly used to refer to the polymkeric substance by two kinds of different monomers preparations) and by the polymkeric substance (for example, terpolymer, tetrapolymer etc.) more than two kinds of different monomers preparations.
Terms such as " catalytic amounts " represents to be enough to promote that the reaction between two or more reactants reaches the amount of the catalyzer that can recognize degree.In the context of the present invention, catalytic amount is the amount that promotes the necessary catalyzer of speed of reaction of silane group on the rate of polymerization of annular siloxane or siloxanes and the matrix polymer.
Terms such as " crosslinked amounts " represents the amount of linking agent or radiation or moisture or any other cross-linking compounds or energy, it is enough to can detect (by any generally acknowledged method giving at least in composition or blend under the crosslinked condition, for example, dimethylbenzene extractable matter etc.) amount is crosslinked.
Thermoplastic polymer
Any thermoplastic polymer that forms the matrix of therein polymerization of annular siloxane can be used for practice of the present invention.Preferably, thermoplastic polymer can be functionalized with silane group.Thermoplastic polymer is characterised in that, they can be melt into liquid and they can be frozen into crisp glassy state when enough cold when heating.A lot of thermoplastic polymers are high molecular weight materials, and it comprises through the chain of weak Van der Waals force combination (for example, polyethylene); And/or show strong dipole-dipole interaction and hydrogen bond (for example, nylon), and/or even the accumulation (for example, polystyrene) of performance aromatic ring.Thermoplastic polymer is different from thermosetting polymer (for example, vulcanized rubber), since different from thermosetting polymer, their again meltings and again molding.A lot of thermoplastic materials are addition polymers; For example, the vinyl chain-growth polymers thing is such as polyethylene and polypropylene.Representational thermoplastic polymer includes but not limited to polyester, polycarbonate, urethane, nylon, polyvinyl chloride and polyolefine.
A particularly preferred analog thermoplastic polymkeric substance that is used as matrix polymer in the present invention's practice is polyolefine.These thermoplastic polymers comprise polyolefin homopolymer and interpretation simultaneously.The example of polyolefin homopolymer is the homopolymer of ethene and propylene.The example of polyolefine interpretation is ethylene/alpha-olefin interpolymers and propylene/alpha-olefins interpretation.Alpha-olefin is preferably C
3-20The alpha-olefin of line style, branching or ring-type (for the propylene/alpha-olefins interpretation, thinking that ethene is alpha-olefin).C
3-20The example of alpha-olefin comprises propylene, 1-butylene, 4-methyl 1-1-amylene, 1-hexene, 1-octene, 1-decene, 1-laurylene, 1-tetradecylene, 1-hexadecylene and 1-octadecylene.Alpha-olefin also can comprise ring texture, such as hexanaphthene or pentamethylene, obtains alpha-olefin, such as 3-cyclohexyl-1-propylene (allyl cyclohexane) and vinyl cyclohexane.Although be not that the standard of this term of alpha-olefin is understood, for purpose of the present invention, some cyclic olefin (such as norbornylene and relevant alkene) is alpha-olefin and can be used for replacing some or all of above-mentioned alpha-olefin.Similarly, vinylbenzene and relevant alkene thereof (for example, alpha-methyl styrene etc.) are the alpha-olefins for the object of the invention.Illustrative polyolefin copolymer comprises ethylene/propene copolymer, ethylene-butylene copolymer, ethene/1-hexene copolymer, ethene/1-octene copolymer, ethylene/styrene multipolymer etc.Illustrative terpolymer comprises ethylene/propene/1-octene copolymer, ethylene/propene/butylene copolymer, ethylene/butylene/1-octene copolymer and ethylene/butylene/styrol copolymer.Multipolymer can be random or block.
The multipolymer that polyolefine also can be comprised of ethene and unsaturated ester or acid, these polyolefine be know and can prepare by conventional pressure technique.Unsaturated ester can be alkyl acrylate, alkyl methacrylate or vinyl esters of carboxylic acids.Alkyl group can comprise 1 to 8 carbon atom, preferably comprises 1 to 4 carbon atom.Carboxylicesters can comprise 2 to 8 carbon atoms, preferably comprises 2 to 5 carbon atoms.Shared ratio can be for 1 to 50 % by weight, based on the weight of multipolymer in multipolymer for the ester comonomer.The example of acrylate and methacrylic ester is ethyl propenoate, methyl acrylate, methyl methacrylate, tert-butyl acrylate, n-butyl acrylate, n-BMA and 2-ethylhexyl acrylate.The example of vinyl esters of carboxylic acids is vinyl-acetic ester, vinyl propionate base ester and butyric acid vinyl ester.The example of unsaturated acid comprises vinylformic acid or toxilic acid.
The more particularly example that is used for olefines interpretation of the present invention (for example, comprises very low density polyethylene (VLDPE)
Ethene/1-hexene polyethylene made by The Dow ChemicalCompany), the even linear ethylene/alpha-olefin copolymer of branching (for example, MitsuiPetrochemicals Company Limited
With Exxon Chemical Company's
), evenly branching the substantial linear ethylene/alpha-olefin polymer (for example,
With
Polyethylene is available from The Dow Chemical Company) and olefin block copolymers, as being described in USP 7,355, those of 089 are (for example,
Available from The Dow ChemicalCompany).Preferred polyolefin copolymer is the linear ethylene multipolymer of even branching and the substantial linear ethylene copolymer of even branching.The substantial linear ethylene copolymer is particularly preferred, and it is described in greater detail in USP 5,272,236,5,278,272 and 5,986,028.
The polyolefin copolymer that is used for the present invention's practice also comprises propylene, butylene and other multipolymer based on alkene, for example, comprises majority and derives from the unit of propylene and the multipolymer that minority derives from the unit of another kind of alpha-olefin (comprising ethene).The propene polymer that is used for the present invention's practice comprises available from The Dow ChemicalCompany's
Polymkeric substance and available from ExxonMobil Chemical Company's
Polymkeric substance.
The blend of any interpretation in the above olefines interpretation also can be used for the present invention, polyolefin copolymer can be with one or more other polymer blendings or with one or more other polymkeric substance dilutions, so that in preferred mode, polyolefin copolymer of the present invention account for blend thermoplastic polymer components at least about 50wt%, preferably account for blend thermoplastic polymer components at least about 75wt%, more preferably account for blend thermoplastic polymer components at least about 80wt%.
Be used for the polyolefine, particularly ethene polymers of the present invention's practice before grafting, its density is typically less than every cubic centimetre of (g/cm of 0.965 gram
3), preferably less than 0.93g/cm
3The density of ethylene copolymer is typically greater than 0.85g/cm
3, be preferably more than 0.86g/cm
3Density is measured by the rules of ASTM D-792.Usually, the alpha-olefin content of interpretation is higher, and the density of this interpretation is lower and more amorphous.The feature of low density polyolefin multipolymer is hypocrystalline, flexible and have a good optical property (for example, high transmission and the low haze of visible light and UV light) usually.
The melt index of ethene polymers before grafting that is used for the present invention's practice is typically greater than per 10 minutes (g/10min) of 0.10 gram, is preferably more than 1g/10min.Polyvinyl melt index is typically less than 500g/10min, preferably less than 100g/10min.(measure by 190 ℃/2.16kg) rules by ASTMD-1238 for melt index.
Preferably, the polyolefin resin for the present invention's practice comprises alkoxysilane groups (being also referred to as silane crosslinker).Typically, alkoxysilane groups grafts on polyolefin resin.Any will with organosilicon polymer effectively the silane of grafting and reaction can be used for practice of the present invention.Suitable silane comprises the unsaturated silane that comprises ethylenic unsaturated alkyl group (such as vinyl, allyl group, pseudoallyl, butenyl, cyclohexenyl or γ-(methyl) acryloyl-oxy allyl group) and hydrolysable group (for example,-oxyl, methanoyl (hydrocarbonyloxy) or alkyl amino group).The example of hydrolysable group comprises methoxyl group, oxyethyl group, methanoyl, acetoxyl group, propionyloxy and alkylamino or arylamino group.Preferred silane is the unsaturated organoalkoxysilane that can be grafted on the polymkeric substance.These silane and their preparation method are described in greater detail in USP 5,266,627.The mixture of vinyltrimethoxy silane, vinyltriethoxysilane, γ-(methyl) acryloyl-oxy propyl trimethoxy silicane and these silane is for preferred silane crosslinker of the present invention.
Replacedly, can use silane copolymer, for example, SILINK
TmPoly-(ethene-copolymerization-vinyltrimethoxy silane) multipolymer, replace with the alkoxysilane groups grafting or otherwise with the olefin polymer of alkoxysilane groups modification or with its combination.
Silane crosslinker grafts on polyolefine by any ordinary method, and typically it is undertaken in the situation that radical initiator (for example, superoxide or azo-compound) exists or by ionizing radiation etc.Organic initiators is preferred, any as in the peroxide initiator, for example, dicumyl peroxide, di-t-butyl peroxide, t-butylperoxyl benzoate, benzoyl peroxide, cumene hydroperoxide, the sad tert-butyl ester of mistake, methyl-ethyl-ketone peroxide, 2,5-dimethyl-2,5-two (t-butyl peroxy) hexane, peroxidation lauryl and t-butyl peroxy-acetate.Suitable azo-compound is azobis isobutyronitrile.The amount of initiator can change, but its amount typically is at least 0.02phr, is preferably at least 0.03phr.Typically, initiator is no more than 0.15phr, and preferably it is no more than about 0.10phr.The ratio of silane crosslinker and initiator can change widely, but typical linking agent: and the ratio of initiator is 10: 1 to 150: 1, is preferably 18: 1 to 100: 1.
Although any ordinary method can be used for silane crosslinker is grafted on polyolefine, preferred method is that fs at reactive extruder (such as the Buss kneader) is with both and initiator blend.The grafting condition can change, but for polyethylene, the melt temperature of grafting typically is 160 to 260 ℃., be preferably 190 to 230 ℃., this depends on the residence time and the transformation period of initiator.
Silane crosslinker or as the group that grafts on polyolefin backbone or when the amount that in silane copolymer, is used for the present invention's practice as being attached to the unit in the polymer chain can be according to the character of polyolefine or silane copolymer, silane, processing conditions, grafting efficiency, the final application and similar factor and changing widely, but typically use at least 0.2wt%, preferably use at least 0.5wt%, based on the weight of multipolymer.Normally to two kinds of key constraints of silane crosslinker maximum usage quantity in the present invention's practice, typically the maximum of silane crosslinker is no more than 5wt% to convenient and economic consideration, and preferably it is no more than 3wt%, based on the weight of multipolymer.
Annular siloxane
The initial substance of ring-opening polymerization is cyclosiloxane (being also referred to as annular siloxane).Useful annular siloxane is the material of knowing and can buy from commerce.They have general formula (R
2SiO)
n, wherein R represent hydrogen or optional replace comprise at the most alkyl, thiazolinyl, aryl, alkaryl or the aromatic alkyl group of 20 carbon atoms, it is 3 to 12 integer that n represents to be worth.R can replace, and for example, is replaced by halogen (such as fluorine or chlorine).Alkyl group can be, for example, and methyl, ethyl, n-propyl, trifluoro propyl, normal-butyl, sec-butyl and the tertiary butyl.Alkenyl group can be, for example, and vinyl, allyl group, propenyl and butenyl.Aryl and aromatic alkyl group can be, for example, and phenyl, tolyl and benzyl.Preferred group is methyl, ethyl, phenyl, vinyl and trifluoro propyl.Preferably, whole R groups of at least 80% are methyl or phenyl groups, most preferably are methyl.Even more preferably, basic all R groups are methyl groups.Preferably, the value of n is 3 to 6, most preferably is 4 or 5.The example of suitable annular siloxane is hexamethyl cyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentaandoxane, five (methyl ethylene) D5, four (phenyl methyl) cyclotetrasiloxanes and pentamethyl-hydrogen D5.A kind of suitable especially material that can buy commercially is the mixture of octamethylcyclotetrasiloxane and decamethylcyclopentaandoxane.Wherein R is methyl, and compound is called Dn; For example, when n=4, compound is called D4 or D
4
Suitable ring-type initial substance comprises cyclosiloxane, other ring compound that it comprises different siloxane units and also comprise other atom or atomic group except siloxanes group in their ring.Example comprises following three kinds of known ring compounds.
Catalyzer
In principle, any phosphazene base is suitable to ring opening catalyst of the present invention.Phosphazene base comprises cored structure P=N, wherein the N free valence bond be connected to hydrogen, hydrocarbon ,-P=N or=P-N, the P free valence bond is connected to-N or-N.Various suitable phosphazene base have been described in Schwesinger et al,
Liebigs Ann.1996,1055-1081.Some phosphazene base can be commercially available from Fluka Chemie AG, Switzerland.Phosphazene base preferably comprises at least three P atoms.Some preferred phosphazene base are materials of following general formula:
((R
1 2N)
3P＝N-)
x(R
1 2N)
3-xP＝NR
2
{((R
1 2N)
3P＝N-)
x(R
1 2N)
3-xP-N(H)R
2}
+{A}
-
{((R
1 2N)
3P＝N-)
y(R
1 2N)
4-yP}
+{A}
-
{(R
1 2N)
3P＝N-(P(NR
1 2)
2＝N)
z-P
+(NR
1 2)
3}{A}
-
R that wherein can be identical or different in each position
1Be hydrogen or the optional hydrocarbyl group that replaces, be preferably C
1-C
4Alkyl group, or wherein be connected in two R of identical N atom
1Group can keyed jointing, obtains heterocycle, is preferably 5 yuan of rings or 6 yuan of rings; R
2Be hydrogen or the optional hydrocarbyl group that replaces, be preferably C
1-C
20Alkyl group, more preferably C
1-C
10Alkyl group; X is 1,2 or 3, is preferably 2 or 3; Y is 1,2,3 or 4, is preferably 2,3 or 4; Z is 1 to 10 integer, is preferably 1,2 or 3; A is negatively charged ion, is preferably fluorine, hydroxide radical, silane alkoxide, alkoxide, carbonate or bicarbonate radical.
Formula { (R
1 2N)
3P=N-(P (NR
1 2)
2=N)
z-P
+(NR
1 2)
3{ A}
-Compound can be by the preparation of following method, described method comprises the phosphonitrile material that makes line style Phosphorates phosphorus Halides nitrile compound (being preferably muriate) and the compound reaction that is selected from secondary amine, metal amide and quaternary ammonium halide form ammonification, and then ion exchange reaction replaces negatively charged ion with nucleophilic reagent.Phosphorates phosphorus Halides nitrile compound and their preparation method are well known in the art; For example, a kind of useful especially method comprises PCl
5With NH
4The reaction of Cl in the situation that suitable solvent exists.Secondary amine is the preferred reagent that is used for the reaction of halogenation phosphonitrile, and suitable secondary amine has formula R
3 2NH, wherein R
3To comprise the at the most hydrocarbyl group of 10 carbon atoms, perhaps two R
3Group all forms the heterocyclic group that comprises nitrogen-atoms, for example pyrrolidino group, pyrrole group or pyridine groups.Preferably, R
3Low-grade alkyl group, more preferably methyl group, perhaps two R
3Group all forms pyrrolidino group.Suitable preferred secondary amine comprises dimethylamine, diethylamine, dipropyl amine and tetramethyleneimine.Preferably, reaction is carried out in the situation that can catch the halid material of exchange (for example, amine is such as triethylamine) existence.The by product (for example, triethyl ammonium chloride) that obtains can be removed from reaction mixture, for example, remove by filtration.Carry out in the situation that reaction can exist in the suitable solvent of phosphonitrilic chloride and line style phosphazene base.Suitable solvent comprises aromatic solvent, such as toluene.Then must make the line style phosphonitrile material that forms by this method move through ion exchange reaction (being preferably ion exchange resin), negatively charged ion is by firmly nucleophilic reagent (be preferably hydroxyl or alkoxyl group, most preferably be hydroxyl) replacement in described ion exchange reaction.Suitable ion exchange system comprises any known ion exchange system, for example, and ion exchange resin, and do not provide more detailed description.Phosphonitrile preferably was dispersed in the suitable medium before moving through ion exchange system.Suitable medium comprises water, alcohol and both mixtures.Particularly preferred for phosphazene base compound of the present invention, R
1Methyl, R
2Be the tertiary butyl or uncle's octyl group, x is that 3, y is 4, and A is fluorine or hydroxide radical.
Method
Method of the present invention is to prepare the reactively blending thing of organosilicon and thermoplastic polymer and the method for multipolymer by the ring-opening polymerization of annular siloxane in polymer thermoplastic matrix.The method itself can be followed a kind of at least three kinds of routes.In the first route, annular siloxane is joined in the thermoplastic polymer annular siloxane experience polymerization and form the reactively blending thing of the siloxanes (that is, organosilicon polymer) of thermoplastic polymer and polymerization under open loop condition.The thermoplastic polymer components of this reactively blending thing is can the Application standard crosslinking technological randomly crosslinked, for example, if thermoplastic polymer is polyolefine, polyolefine is contacted under crosslinked condition with superoxide.The open loop of annular siloxane can be promoted through using ring opening catalyst.
In the second route, annular siloxane (is for example joined silane-functionalised thermoplastic polymer under open loop condition, polyolefine) in, annular siloxane stands polymerization and is formed with organosilicon polymer, and then the reaction of the silane group of organosilicon polymer and thermoplastic polymer forms reactive copolymerization product thus.The necessary condition of reaction between the silane group of promotion organosilicon polymer and thermoplastic polymer is basic identical with the necessary condition of open loop that promotes annular siloxane.As in the first route, the open loop of annular siloxane can promote with ring opening catalyst, typically after reclaiming reactive copolymerization product from reaction mixture, can make polymer thermoplastic matrix crosslinked.
In the third route, with annular siloxane and silane crosslinker under the condition of open loop and Silane Grafted (in this case, the condition of open loop is a kind of condition and identical with the condition of Silane Grafted) join in the thermoplastic polymer, the annular siloxane polymerization, silane crosslinker grafts on thermoplastic polymer in this identical operating process simultaneously, and then the reaction of the silane group of organosilicon polymer and thermoplastic polymer forms reactive copolymerization product.As in the first and the second route, the polymerization of annular siloxane can promote with catalyzer, typically after reclaiming reactive copolymerization product from reaction mixture, can randomly make polymer thermoplastic matrix crosslinked.
Although the equipment of preparation feedback blend and copolymerization product of being used for is not crucial to the present invention, typically these products prepare in the mixing device that can impose to reaction mixture shearing action.The example of mixing device is inner batch mixer, such as Banbury
TMOr Bolling
TMInternal mixer.Replacedly, can use continuous single screw rod or double-screw mixer, such as Farrel
TMContinuous mixing device, Werner and Pfleiderer
TMDouble-screw mixer or Buss
TMMediate continuous extruder.The type of employed mixing tank and the operational condition of mixing tank will affect the character of composition, such as viscosity, volume specific resistance with extrude surface flatness.
The thermoplastic polymer that typically will comprise silane functionality is fed in the forcing machine, then annular siloxane is fed in the forcing machine, if use, ring opening catalyst and any other operable processing additives can be fed in the forcing machine.Make reaction mixture stand open loop condition, described condition comprises the temperature of thermoplastic polymer fusing point to 200 ℃ (for polyolefine), definite temperature depends on the quantity of different variablees, and a variable in the described different variablees is: open loop whether in mixing process, in the course of processing or occur in the last handling process.Pressure can be for subatmospheric to super-atmospheric pressure.In extruder, pressure can approach or (70 megapascal (MPa)s, mPa), and in uncovered batch mixer, pressure typically is environmental stress (0.1mPa) above 10,000psi.
If the Silane Grafted of thermoplastic polymer is carrying out in the annular siloxane open loop operation identical with polymerization, then this can be undertaken by one of following two kinds of methods.A kind of method is to use long forcing machine, and it is equipped with the Silane Grafted zone, then is that open loop/polyreaction is regional.Replacedly, Silane Grafted and organosilicon reaction can almost occur simultaneously.Yet from the position of technology control chemistry, preferred mode is to use to begin with silane-functionalised thermoplastic polymer, such as SI-LINK
TMMultipolymer or PE-g-VTMS (with the polyethylene of vinyltrimethoxy silane grafting).
The content of annular siloxane in reaction mixture typically is 0.1 to 85 weight percent (wt%), is preferably 0.2 to 20wt%, based on the weight of reaction mixture.The content of thermoplastic polymer in reaction mixture typically is 15 to 99.9wt%, is preferably 10 to 95wt%, based on the weight of reaction mixture.If really exist, then the amount of catalyzer in reaction mixture is that 10 parts per 1,000,000 parts (ppm) are to 5wt%, based on the weight of reaction mixture.
In those situations, (for example namely in polyolefine-organosilicon reaction blend or multipolymer, expect the organosilicon of relative high-content, at least 5wt%, gross weight based on thermoplastic polymer and organosilicon polymer), can be desirably in and add more before the polycyclic organosilicon, the annular siloxane that adds many multiple doses with the dosage that allows the initial stage partly or entirely reaction advance in the system.This helps avoid a potential technique difficult problem relevant with a large amount of annular siloxane (it much is liquid).
Negatively charged ion or positively charged ion ring-opening polymerization can occur, and exist the kinetics of reaction product or the selection of thermodynamic control (by selecting organosilicon, catalyzer and other condition).According to the character of initiator, in the existence of active anion end group or non-existent situation, can form monohydroxy or dihydroxyl organosilicon.Therefore, the organosilicon that obtains and intermediate can be easy to participate in the functionalization and crosslinking reaction with the thermoplastic polymer of Silane Grafted.
In open loop/polymerization process, add organosilicon functional group and can be used for giving other character.The organosilicon that for example, can add some vinyl-functional is attached in the organosilicon polymer to promote peroxide crosslinking it.In addition, can provide end group, for example, shown in following equation.
Me
3SiOSiMe
3+n(Me
2SiO)
4→Me
3SiO(Me
2SiO)
4nSiMe
3
Wherein Me is methyl, and n is the add-on of annular siloxane.Me
3SiOSiMe
3With (Me
2SiO)
4Ratio determine the organosilyl stoichiometry that obtains, Me
3SiOSiMe
3(Me
2SiO)
4Total amount determine that organosilicon is with respect to the amount of thermoplastic polymer.
Branch point can be incorporated in the organosilicon polymer by adding T or Q group (the most frequently used polydimethylsiloxane is comprised of the D group as repeating unit).These groups such as following schematically showing.
Can provide to control by the various sources that add the M unit M group of molecular weight and chain length,
Described M unit comprises the organosilicon of hexamethyldisiloxane (hexamethyldisolaxane) or short methyl blocking, and its release M or MM end group are together with the other D group of minority.
Reactively blending thing of the present invention and multipolymer can comprise other additive, and it includes but not limited to antioxidant, solidifying agent, crosslinking coagent, synergistic agent and delayer, processing aid, filler, coupling agent, uv-absorbing agent or stablizer, static inhibitor, nucleator, slip(ping)agent, softening agent, lubricant, viscosity modifier, tackifier, antiblocking agent, tensio-active agent, extending oil, acid scavenger and metal passivator.The usage quantity of additive can for less than 0.01wt% to greater than 10wt%, based on composition, that is, the weight of reactively blending thing or copolymerization product.
The example of antioxidant is as follows, but is not limited to: hindered phenol, such as four [methylene radical (3,5-, two-tertiary butyl-4-hydroxy hydrogenation-laurate)] methane; Two [(β-(3, the 5-di-tert-butyl-4-hydroxyl benzyl)-the methyl carboxy ethyl)] thioether, 4,4 '-thiobis (2-methyl-6-tert-butylphenol), 4,4 '-thiobis (the 2-tertiary butyl-5-methylphenol), 2,2 '-thiobis (4-methyl-6-tert-butylphenol) and sulfenyl di ethylene bis (3,5-di-t-butyl-4-hydroxyl) hydrogenated cinnamate; Phosphorous acid ester and phosphinate are such as tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester and di-tert-butyl-phenyl-phosphinate; Thio-compounds is such as thiodipropionate dilauryl, thio-2 acid myristyl ester and thio-2 acid distearyl ester; Various siloxanes; 2 of polymerization, 2,4-trimethylammonium-1,2-dihydroquinoline, n, n '-two (1,4-dimethyl amyl group-Ursol D), alkylating pentanoic, 4, the diaryl-Ursol D of 4 '-two (alpha, alpha-dimethylbenzyl) pentanoic, phenylbenzene-Ursol D, mixing and other hindered amine anti degradant or stablizer.The usage quantity of antioxidant can be for 0.1 to 5wt%, based on the weight of composition.
The example of solidifying agent (being cross-linked evocating agent for polyolefine for example) is as follows: dicumyl peroxide; Two (α-tertiary butyl-peroxy isopropyl base) benzene; Sec.-propyl cumyl tert-butyl peroxide; The tert-butyl peroxide cumyl; Di-t-butyl peroxide; Two (t-butyl peroxy)-2 of 2,5-, the 5-dimethylhexane; Two (t-butyl peroxy)-2 of 2,5-, 5-dimethyl hexin-3; Two (t-butyl peroxy) 3,3 of 1,1-, the 5-trimethyl-cyclohexane; Sec.-propyl cumyl cumyl peroxide; Peroxidation two (sec.-propyl cumyl); Or its mixture.The usage quantity of peroxide firming agent can be about 0.1wt% to 5wt%, based on the weight of composition.Can use various other known auxiliary curing agents, synergistic agent and delayer, such as the tricarbimide triallyl ester; The ethoxylation bisphenol a dimethacrylate; α-methylstyrenedimer; Be described in USP 5,346, other auxiliary agent of 961 and 4,018,852.
The example of processing aid includes but not limited to: the metal-salt of carboxylic acid, such as Zinic stearas or calcium stearate; Lipid acid is such as stearic acid, oleic acid or erucic acid; Fatty amide, such as stearylamide, oleylamide, erucicamide or N, N '-ethylenebisstearamide; Polyethylene wax; The polyethylene wax of oxidation; The polymkeric substance of oxyethane; The multipolymer of oxyethane and propylene oxide; Vegetable wax; Petroleum wax; Nonionogenic tenside; And polysiloxane.The usage quantity of processing aid can be for 0.05 to 5wt%, based on the weight of composition.
The example of filler includes but not limited to clay, precipitated silica and silicate, steam deposition of silica, calcium carbonate, thin mineral and carbon black.The usage quantity of filler can for less than 0.01wt% to greater than 50wt%, based on the weight of composition.
The example of fire retardant includes but not limited to magnesium hydroxide, aluminium hydroxide, huntite, hydromagnesite, ANTIMONY TRIOXIDE SB 203 99.8 PCT, potassium hydroxide, calcium phosphate, zirconium white, titanium oxide, zinc oxide, magnesium oxide, magnesiumcarbonate, calcium carbonate, barium sulfate, barium borate, barium metaborate, zinc borate, zinc metaborate, aluminium acid anhydride (aluminumanhydride), molybdenumdisulphide, clay, red phosphorus, diatomite, kaolinite, montmorillonite, hydrotalcite, talcum, silica, hard charcoal (white carbon), C ore deposit (celite), asbestos, and lithopone.Magnesium hydroxide and aluminium hydroxide are preferred fire retardants.
Use
The application that organosilicon-thermoplastic polymer (particularly organosilicon-polyolefine) reactively blending thing and copolymerization product by the inventive method preparation can needing be used for following character: thermostability, ozone resistance and weathering resistance, oxidative stability, oilness, water-repellancy, low surface tension, good electrical properties, cryogenic properties, oil resistant, moisture and steam, chemical resistant properties and/or flame retardant resistance.Such application comprises: sparking plug protective guard (boots) and igniting irdome (ignition wire jackets); Scatterer and the heating hose of vehicle front propeller shaft sleeve, packing ring, sealing member (seals), O shape ring, protective coating and truck and motorbus; Polymer power transmission isolator and cable components (joint and terminal organ and outdoor insulative body); Cable sheath and insulation comprise fire-retardant kind.
Reactively blending thing of the present invention and multipolymer also can be used as expanding material.For example, often organosilicon is joined in the polyolefine to give various favourable character.Typically, organosilicon not with the polyolefine highly compatible, this can cause poor morphology and generation to be oozed out.A kind of morphology of organosilicon and polyolefinic blend that can make that comprises in a small amount of multipolymer of the present invention or the reactively blending thing improves.In addition, adding a kind of in these a small amount of multipolymers or the reactively blending thing in the polyolefinic reactive processing process of organosilicon and polyolefine or Silane Grafted can provide the speed of reaction of raising and the morphology of enhancing, and this is because the mixing of the improvement that can produce from compatible role.In some cases, at first in solution, prepare expanding material to guarantee fully mixing and morphology.Probably only need a small amount of such expanding material.
The ring-opening polymerization of octamethylcyclotetrasiloxane provides the method for the multipolymer of formation siloxanes-thermoplastic polymer (particularly organosilicon-polyolefine) grafting.This method can be better than the condensation of silanol stopped polydimethyl silane (PDMS) on some degree, because it allows the larger control to reaction product.For example, cause or catalyzed reaction by use-OH or H+, can obtain the PDMS chain of two senses, it is by two oh group end-blockings.This product can form crosslinked multipolymer with the polyolefine reaction of VTMS grafting subsequently.On the other hand, only by selecting different catalyzer (for example, carbanion), the PDMS chain of simple function can form.Then this chain can graft on the Trimethoxy silane group, and that blend remains generally is thermoplastic.
Following embodiment illustrates various embodiment of the present invention.Unless illustrate, otherwise all parts and per-cent are all based on weight.
Particular implementation
Can follow the tracks of with the FTIR spectrography degree of octamethylcyclotetrasiloxane (D4) polymerization.As from following embodiment and Fig. 1 as seen, D4 (top curve) has shown at about 1075cm
-1That locates is unimodal.The initial initial sign of polymerization is little acromion (bottom curve) to occur on the right side at D4 peak.Along with the carrying out of polymerization, this little acromion increases, and D4 is unimodal in its growth reduces.This will continue until the peak of two amplitudes such as about appears at 1010cm
-1And 1095cm
-1This is the signal of PDMS chain formation.
Carry out two Brabender mixing tanks and react to investigate open loop/polymerization of use D4 as the feasibility of the method for the multipolymer that forms the grafting of PDMS/ polyolefine.In a sample, (its density is 0.87g/cm to make ethylene-octene copolymer
3Melt index is 5 (measuring according to ASTM D1238), and derives from The Dow Chemical Company) with VTMS (about 1.5 % by weight are based on polyolefinic weight) grafting, then its D4 with 5% is soaked, until there is not obvious liquid residue.The pellet that obtains is joined the Brabender mixing tank of 100 ℃ and 45 RPM.Allow blend to reflux two minutes, then add P4-tertiary butyl phosphazene base solution (the 1-tertiary butyl-4,4,4-three (dimethylamino)-2, two [three (dimethylamino) phosphorane fork is amino]-2 of 2-of the 0.25M of 0.1mL
5, 4
5-chain type two (phosphonitrile) (1-tert-butyl-4,4,4-tris (dimethylamino)-2,2-bis[tris (dimethylamino) phosphor-anylidenamino]-2
5, 4
5-catenadi (phosphazene)), derives from Sigma-Aldrich, the FlukaAnalytical of Inc.).Allow D4 reaction 15 minutes, then it is removed from the Brabender mixing tank.Second sample uses 140 ℃ temperature and the catalyzer (0.25M) of 0.2mL to carry out.Its Blending Processes (RPM, reaction times) is identical with the Blending Processes of first sample.
Two experiments have all shown obvious expected response.Carry out FTIR at the compacting film, for two samples, at about 1025cm
-1The initial of acromion at place all is obvious.The FTIR spectrum of second sample as shown in Figure 2.The top curve has been described initial FTIR, and it has also shown the D4 of significant quantity.The D4 evaporation is spent the night, then record middle part curve.At 1090cm
-1The residual peak at place is because from the absorption (bottom curve) of the EG 8200 of VTMS grafting.
Although described in detail the present invention in above description, drawings and Examples, this detailed description is the purpose for explanation.In the situation that does not deviate from the spirit and scope of the present invention, those skilled in the art can much change and change, and the spirit and scope of the present invention such as claims are described.
Claims (7)
1. the method for a preparation feedback blend, wherein said blend comprises the organosilicon polymer in the polymer thermoplastic matrix, said method comprising the steps of: (A) form annular siloxane and the poly mixture that comprises silane functionality, and (B) make described mixture stand to make described annular siloxane polymerization to be formed with the condition of organosilicon polymer.
2. one kind prepares to comprise and derives from polyethylene, the method of the copolymerization product of the unit of silane crosslinker and organosilicon polymer, said method comprising the steps of: described silane crosslinker is contacted under the grafting condition with described polyethylene, so that described silane crosslinker grafts on described polyethylene, (B) under the annular siloxane polymerizing condition, annular siloxane is joined in the polyethylene of described Silane Grafted, so that described organosilicon polymer forms and be combined with the polyethylene of described Silane Grafted and form described copolymerization product, wherein said silane crosslinker is at least a in the following material: vinyltrimethoxy silane, vinyltriethoxysilane, the mixture of two or more in γ-(methyl) acryloyl-oxy propyl trimethoxy silicane and these silane.
3. one kind prepares to comprise and derives from polyethylene, the method of the copolymerization product of the unit of silane crosslinker and organosilicon polymer, said method comprising the steps of: make simultaneously described polyethylene, described silane crosslinker and annular siloxane contact in described poly matrix with under grafting and open loop and polymerizing condition, so that described silane crosslinker grafts on described polyethylene, described annular siloxane polymerization forms described organosilicon polymer, described organosilicon polymer and then be combined with the polyethylene of described Silane Grafted and form described copolymerization product, wherein said silane crosslinker are at least a in the following material: vinyltrimethoxy silane, vinyltriethoxysilane, the mixture of two or more in γ-(methyl) acryloyl-oxy propyl trimethoxy silicane and these silane.
4. each described method among the claim 1-3, the polymerization of wherein said annular siloxane promotes with catalyzer.
5. the method described in the claim 4, wherein said catalyzer is phosphazene base.
6. the method described in the claim 5, wherein said annular siloxane are at least a in the following material: hexamethyl cyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentaandoxane, five (methyl ethylene)-D5, four (phenyl methyl) cyclotetrasiloxane and pentamethyl-hydrogen-D5.
7. the method described in the claim 2, wherein said first step carries out in the grafting zone of extruder, carries out in the open loop/zone of convergency of described identical extruder with described second step.
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| PCT/US2009/051610 WO2010014499A2 (en) | 2008-08-01 | 2009-07-24 | Silicone-thermoplastic polymer reactive blends and copolymer products |
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| US9394483B2 (en) | 2012-05-24 | 2016-07-19 | Sabic Global Technologies B.V. | Flame retardant polycarbonate compositions, methods of manufacture thereof and articles comprising the same |
| US9023922B2 (en) | 2012-05-24 | 2015-05-05 | Sabic Global Technologies B.V. | Flame retardant compositions, articles comprising the same and methods of manufacture thereof |
| JP5894710B2 (en) * | 2012-09-27 | 2016-03-30 | ダウ グローバル テクノロジーズ エルエルシー | Method for reducing peroxide migration in crosslinkable ethylene polymer compositions |
| JP6882192B2 (en) * | 2015-04-30 | 2021-06-02 | ダウ グローバル テクノロジーズ エルエルシー | Hydroxy-terminated PDMS as a curing control additive for silane cross-linking of polyolefins |
| CN108368325A (en) | 2015-09-30 | 2018-08-03 | 塞拉尼斯销售德国有限公司 | The sub-assembly of low friction the is stingless power of hearing |
| US11459411B2 (en) | 2017-06-29 | 2022-10-04 | Dow Global Technologies Llc | Polyolefin composition |
| WO2019023008A1 (en) | 2017-07-25 | 2019-01-31 | Dow Silicones Corporation | Method for preparing a graft copolymer with a polyolefin backbone and polyorganosiloxane pendant groups |
| CN111315810A (en) | 2017-10-17 | 2020-06-19 | 塞拉尼斯销售德国有限公司 | Flame retardant polyamide composition |
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- 2009-07-24 CA CA2906561A patent/CA2906561C/en not_active Expired - Fee Related
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- 2009-07-24 WO PCT/US2009/051610 patent/WO2010014499A2/en active Application Filing
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- 2009-07-24 EP EP09790784.4A patent/EP2307484B1/en not_active Not-in-force
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| WO2010014499A3 (en) | 2011-09-15 |
| WO2010014499A2 (en) | 2010-02-04 |
| CN102216372A (en) | 2011-10-12 |
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| EP2307484A2 (en) | 2011-04-13 |
| CA2906561C (en) | 2016-10-11 |
| EP2460841A1 (en) | 2012-06-06 |
| US20110136979A1 (en) | 2011-06-09 |
| CA2906561A1 (en) | 2010-02-04 |
| CA2732755A1 (en) | 2010-02-04 |
| MX2011001293A (en) | 2011-04-14 |
| CA2732755C (en) | 2016-10-11 |
| KR20110043726A (en) | 2011-04-27 |
| EP2307484B1 (en) | 2018-08-22 |
| US8426519B2 (en) | 2013-04-23 |
| EP2460841B1 (en) | 2016-07-13 |
| TW201016753A (en) | 2010-05-01 |
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